Chromium oxide-tungsten oxide-iron oxide gel catalyst



Patented June 17, 1952 CHROMIUM OXIDE-TUNGSTEN OXIDE-IRON OXIDE GEL CATALYST Edward 0. Jacobs, San Mateo, Calif., and Lester G. Lundsted, Grosse Ile, Mich., assignors to Wyandotte Chemicals Corporation, Wyandotte,

Mich., a corporation of Michigan No Drawing. Original application July 23, 1949,

Serial No. 106,505. Divided and this application August 30, 1951, Serial No. 247,189

2 Claims. (01. 252-470) The present application is a division of our pending application, Serial No. 106,505 filed July 23, 1949, which in turn is a division of our copending application Serial No. 733,976, Patent No. 2,503,050, filed March 11, 1947. This invention relates to a chromic oxide complex catalyst composition whichis particularly suited for the aldehydoisomerization of alkylene alpha oxides.

In the co-pending U. S. patent application Serial No. 588,710, now U. S. Patent No. 2,479,632, filed April 16, 1945 by Lester G. Lundsted, Edward J. Schwoegler and Edward C. Jacobs, said Lundsted and Jacobs being co-applicants herein, it is disclosed that a chromic oxide gel catalyst (prepared as described in Vol. 63, p. 1129 of the Journal of the American Chemical Society) effects the isomerization of propylene oxide to allyl alcohol, propionaldehyde being the minor and lesser-proportion product. In other words, in theaforesaid co-pending application, the employment of the chromic oxide gel catalyst alone produced an alkylene oxide isomerization in which the ratio of allyl alcohol to the propionaldehyde was on the order of 3 to 1. We have now discovered, that by the incorporation of oxides of tungsten and iron, this relationship can be reversed; and even to the point where, in the case of propylene oxide, there is practically no allyl alcohol and the propionaldehyde constitutes over 90% of the conversion products. The isomerization process and catalyst composition of our invention also results in exceptionally high and favorable conversion percentages.

The catalyst compositions of our invention are also particularly useful and advantageous in that they possess relatively long lives of activity; and upon regeneration treatment, have the ability of resuming or recapturing an activity paramount to that of the originally prepared catalyst composition.

Briefly outlined, our invention comprises a catalyst composition consisting of a dried or dehydrated chromic oxide gelito which there has been added tungsten oxide and iron oxide. Tungsten oxide and iron oxide, just as in the case of the parent chromic oxide (called chromium oxide by Turkevich et al. in their aforesaid publication in the Journal of the American Chemical Society, Vol. 63, p. .1129) are present as a derivative of a soluble Cr-, W-, or Fe-, salt or oxy-acid subsequently converted to the precipitated metallic oxide by treatment with ammonium hydroxide.

Preferably, the proportions of the abovenamed metallic compound ingredients of ourgel catalyst composition, are found to fall in certain specified ranges. The determination of the proportion of these compounds isconveniently based upon a calculation of the chemically equivalent weights of the corresponding metallic compounds employed in the synthesis of the catalystcompositions, and thence. reduced to simplified or empirical chemical formulas, such as C12Q3,, WO3 and F6203; and even though the actual chemical structure of the metallic compound components of the catalyst compositions is presently unknown, escaping precise chemical analysis. Thus, the preferred range of proportions of these ingredients is as follows: CIzOa, 40-70% by weight; W03, 15-50%; and F6203, 13%. 1 U

The catalyst of our invention need not be admixed with, supported upon, or carried by a socalled catalyst carrier, but is placed directly in a furnace or heating chamber (preferably mounted in a vertical position) with externally applied heat, and the vaporized or gaseous alkylene oxide then passed over and through the heated catalyst.

The following examples further illustrate our invention.

EXAMPLE 1 In this example, the compounds added to the parent chromic oxide gel catalyst, were tungsten oxide and iron oxide. The preparation was as follows:

Nine hundred grams of C1(NO3)3.9H2O, 10 grams of ferric ammonium oxalate and 300 grams ammonium acetate were dissolved in 3 liters of distilled water and the mixture stirred, heated to boiling and then permitted to cool. On cooling, an ammoniacal solution of tungstic acid containing grams of WOaHzO, 816 cc. of concentrated ammonium hydroxide (28% NH: content) and 2.2 liters of distilled water was added, the solution being stirred for 1 minute with subsequent gelation. The resultant gel was baked for 48 hours at 50 C. and washed with distilled water to remove N03 ions. One hundred grams of tungstic acid, dissolved in concentrated am- 3 monium hydroxide were then added to the washed gel and the resultant composition baked to dryness in an oven at 240 C.

The composition of the resultant catalyst was calculated to be:

CrzOa, 51 mols or 49.6% by Weight W03, 33.3 mols or 49.4% by weight F6203, 1 mol or 1.0% by weight 4 cent of furnace products 57.5% propionaldehyde and 4.8% unsaturates.

EXANEPLE4 In the catalyst composition employed in this example, the proportions of tungsten oxide and iron oxide were increased. This catalyst was prepared as follows:

A mixture of 450 grams of CI(NO3)3.9H2O,

Propylene. alpha oxide was passed over this 150 grams of ammonium acetate and 33.9 grams catalyst at a temperature of 350 C. and at a fFe(NO3)a.9I-IzO were dissolved in 1 liters of s ace velocity or 95 grams per hour per liter of. Wat r. at d o h boiling p nt and c l d; catalyst. The conversion, on the basis of the whereupon 4 0 o c c ed ammo um total amount of propylene. alpha oxide fed hydroxide (28% NH: content) were added, through the heated catalyst chamber was.3.6% to forming a gel. The resultant gel was baked propionaldehyde (based on. carbonyl analysis), in an oven at 58 C. for 48 hours. then washed 6% tounsaturates, as allylalcohol. free. of" nitrate ions, drained and a solution of EXAMPLE 2 40; grams of. tungstic acid in 150 cc. concentrated 1 ammonium hydroxide solution was stirred in.

In the catalyst composition employed in. this The resultant mixture was then baked at 250 C. example, the relative proportions of tungsten oxfoi: approximately 96 hours, producing a hard, ide and iron oxide added to the parent chromic black product, which was thereafter heated to oxide gel, were reduced. The preparation of the 450 C. for 3 hours. catalyst composition was similar to that previous- The resultant catalyst composition contained ly described in Examplel. The resultant compo- 5 the following (calculated basis): sition, ona calculated basis, contained: crzos 132 m 018 or 67.8% by Weight CrzOa, 5'1 mols or 69.7% by weight W03, 3.8 mols or 29.4% by weight W03, 13.7 mols or 28.7% by weight F6203, 1 mol or 2.8% by'weight Fezoai 1 mol or 15% by welght On passing propylene alpha. oxide over the On. passing, propylene alpha oxide over the above described catalyst composition at a temabove. catalyst. at. a temperature of 350 C. and perature of 350 C. and at a space velocity of at: a space velocity of 110 grams per. hour per 296 grams per hour. per liter of catalyst. the 1iterocatalyst,.thefurnace products. were found furnace products contained 55.6% propionaldeto. contain. 63%, propionaldehyde and 17% unhyde and 8.7% unsaturates. saturates. For the purpose. of summarizing the foregoing Examples l-4 inclusive the following table is 3 given showing the. respective. amounts. of catalyst In the catalyst p si n mp oy d in th s composition ingredients, and the per cent of the examp the Same catalyst o Example 1 a propionaldehyde. (based on carbonyl analysis) used c p that efter'baking o y s in a and of unsaturates, as allyl alcohol, of the furovenat 240 0;, the dried gel was subsequently nace products, heated'to a te perature of 1000'-1200 C. Nine From this table, it will be seen that the proty-cc..off the resultant heated catalyst (i. e. 51 plonaldehyde. constit t th major and mols CrzOs, 33.3 mols W03, and 1 mol FezOa) dominant product in each case, with the unwereplaced' in the tubular furnace. Propylene saturates (analyzed as allyl alcohol) being in alpha. oxide passed over this catalyst. composia minor proportion. In the majority of cases tion at a temperatureof 214-292 C. (temperathe ratio of the propionaldehyde to unsaturates ture readingstaken at increments of 1 inch apart (of. Examples 1, 2 and 4), is 6 to l or greater. through, a 6%. inch depthof catalyst bed), and It will. also be seen that the percentage proporat' a space velocity of 7.08 grams per hour per tions of catalyst constituents confirm the preliter of catalyst. After so passing'the vaporized ferred range of proportions stated at the outset propylene alpha oxide over the heated catalyst of this description.

Table Example 1 Example 2 Example 3 Example 4 Constituents M01 PenCent M01 Per Cent M01 PerCent M01 Per Cent Ratio g g .Ratio g g Ratlog Ratio ig 01,04.................. 51 49.6' 51.0 69.7 51 49.0 13.2 .s i-2. ii:::::::.::: .3: ?:8 2:? it i; ?:3 ?:2 i3 ti PER CENT or FURNACE PRODUCTS Propioneldehyde... 36. 0 63; 0 67. 5' I55. 6 Unsatumtes 6.0 17.0 4.8 2.7

tor a; periodot 4. hours and 20 minutes, the following. results were obtained: 66.3% conversion of. propylene alpha oxide fed of which. conversion. products 86.8% was propionaldehyde and 7.35% was unsaturates; or on. the basis of per.

Other modes of applying the. principle of our invention may be employed, changes being made as regards to the details described, provided the features stated in any of the following claims or the equivalent of. suchv be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. A chromic oxide complex catalyst composition consisting of a washed and dried aqueous ammoniacal gel consisting of a mixture of chromic oxide, tungsten oxide and iron oxide wherein these ingredients are present in the mol ratios j; of 13.2-51.0 mols chromic oxide, 3.8-33.3 mols tungsten oxide and approximately 1 mol of iron oxide.

2. A chromic oxide complex catalyst composition consisting of a washed and dried aqueous 6 ammoniacal gel consisting of a mixture of chromic oxide, tungsten oxide and iron oxide present in the mol ratios of 13.2-51.0 mols of chromic oxide, Bil-33.3 mols of tungsten oxide and approximately 1 mol of iron oxide, said dried and heated gel being subsequently heated "at a temperature of above 1000 C.

EDWARD C. JACOBS. LESTER G. LUNDSTED.

No references cited. 

1. A CHROMIX OXIDE COMPLEX CATALYST COMPOSITION CONSISTING OF A WASHED AND DRIED AQUEOUS AMMONIACAL GEL CONSISTING OF A MIXTURE OF CHROMIC OXIDE, TUNGSTEN OXIDE AND IRON OXIDE WHEREIN THESE INGREDIENTS ARE PRESENT IN THE MOL RATIOS OF 13.2- 51.0 MOLS CHROMIC OXIDE, 3.8-33.3 MOLS TUNGSTEN OXIDE AND APPROXIMATELY 1 MOL OF IRON OXIDE. 